Polymeric halophors

ABSTRACT

A stable iodine complex formed from the association of iodine with a pyrrolidonyl surfactant and its use in therapeutic, environmental and industrial applications and particularly as low foaming disinfectants for gradual release of iodine over significantly extended periods.

This is a division of application Ser. No. 021,284, filed Mar. 3, 1987.

Iodine complexes with methyl pyrrolidone for germicidal and disinfectantapplications has long been known. However, the iodine disinfectantproperties of this complex is dissipated in a relatively short period sothat reapplication of the disinfectant treatment is required forprotection over long periods. Also, for certain applications, e.g.washing of contaminated equipment, hospital surroundings and animaldisinfection, cleaning as well as germicidal, virucidal and sporicidalproperties are required. Iodine/polyvinyl pyrrolidone complexes, whichpresent numerous complexing sites in the molecule, have been developedfor this purpose and, while these polymeric complexes, do in fact,extend the effective release of iodine over longer periods, they, likethe methyl pyrrolidone/iodine complexes, lack the desired surfactant anddetergent properties. Therefore, it is an aim of research to develop adisinfectant or germicide having extended iodine release time as well asnon-foaming surfactant and cleaning properties so that such treatmentneed not be frequently repeated and removal of other soil or debris canbe accomplished in a single washing treatment.

Accordingly it is an object of this invention to accomplish the abovesought for needs.

Another object of this invention is to provide the release of iodineover an extended period of time by a method which is commerciallyfeasible and economical.

Another object is to provide a low foaming surfactant which inherentlypossesses disinfectant properties.

These and other objects of the invention will become apparent from thefollowing description and disclosure.

The above and other objects and benefits are achieved by providingiodine or bromine complexes of a pyrrolidonyl alkyleneoxy polymerwherein the halogen is complexed with the pyrrolidone ring as well asthe alkyleneoxy group in the polymer chain. More specifically, thecompounds of this invention are the halogen complexes of pyrrolidonylalkyleneoxy polymers which possess high skin substantivity and excellentdisinfectant, bactericide, sporicidal, virucidal and surfactant andcoating properties.

The complexing polymers of this invention are those containing analkyleneoxy pyrrolidonyl unit of the type: ##STR1## wherein R⁴ is H orCH₃ ; a has a value of 1-3; m has a value of 0 or 1 and p has a value of1 or 2, said polymers also containing at least one or more hydrophobicgroups. Generally, the polymeric complexing agents contain anethyleneoxy group, referred to herein as EO, and/or a propyleneoxygroup, referred to herein as PO in the polymer chain.

The halogen complexes of the present invention are iodophors orbromophors and, where complexing takes place, stable complexed sites areformed. The halogen present in the complexed copolymer as availableiodine or bromine can range between about 2% and about 40%, preferablybetween about 5% and about 25%, depending on the amount of disinfectantproperties desired in the product.

Representative species of the pyrrolidonyl alkyleneoxy block copolymerswith which iodine or bromine can be complexed, include the followingtypes C-F. ##STR2## wherein at least one of R² and R³, when present inthe copolymer, is methyl; the remaining of groups R² and R³, whenpresent in the copolymer, being either hydrogen or methyl; R¹ is alkylhaving from 6 to 20 carbon atoms; Y is alkyl having from 1 to 4 carbonatoms; v has a value of 0 to 2; each of h and q have a value of from 0to 100 and at least one of h and q is a positive integer, preferably aninteger greater than one. ##STR3## wherein R⁴, m and p are as definedabove; and g, h, k, n, q, s, t, u, v, w and x are integers having thefollowing values

    ______________________________________                                        g = 0 or 1;        s = 2 to 200;                                              h = 0 to 100;      t = 2 to 50;                                               k = 2 to 200;      u = 2 to 50;                                               n = 1 to 100;      v = 0 to 2;                                                q = 0 to 100;      w = 1 to 25 and                                                               x = 1 to 25.                                               ______________________________________                                    

Since these units may occur in block or random distribution in thepolymeric product, it is to be understood that their subscripts in theformulae represent the total number of designated units in the polymerand not the order of unit succession; although these units may occur inblock segments as indicated above.

Preparations for the above polymers C-E are known. Specifically, thepolymers of Group C where q and m are zero, and h is a positive integerare prepared by reacting an alkyleneoxylated alkylphenol with anepoxyalkyl-2-pyrrolidone or, when m has a value of 1 and p has a valueof 2, by reacting an alkyleneoxylated alkylphenol with the glycidolether of N-hydroxyethyl pyrrolidone, at a temperature of between about100° C. and about 150° C. for 0.5 to 5 hours under atmospheric pressure.When m is a positive integer the polymer is prepared by reacting analiphatic or aromatic alcohol with glycidyl ether ofN-hydroxyethylpyrrolidone under the above conditions. When q is apositive integer, either of the above products are further reacted withthe corresponding alkylene oxide under the above conditions.

The polymers of Group D are prepared by reacting 2-pyrrolidone with analkylene oxide, such as propylene oxide in the presence of an alkalimetal hydroxide, e.g. sodium hydroxide at a temperature between about110° C. and about 175° C. under 15 to 50 psig. for a period of fromabout 0.5 to about 10 hours. When PO and EO units in the polymer aredesired, the above product of Group D is further reacted with theappropriate alkylene oxide at a temperature of between about 110° C. andabout 175° C. under 15 to 50 psig. for a period of from about 0.5 toabout 10 hours.

The polymers of Group E are prepared by reacting polypropylene glycolwith epoxypropylpyrrolidone or the glycidyl ether ofN-hydroxyethylpyrrolidone at a temperature of between 100° C. and about150° C. under from about 14 to about 50 psig. for a period of from about0.5 to about 10 hours.

As in copending application Ser. No. 020,841, now U.S. Pat. No.4,698,412, filed concurrently herewith, the polymers of Group F can beprepared by reacting a poly(N-pyrrolidonyl methyl)ethylene glycol withpropylene oxide or a combination of propylene oxide and ethylene oxideunder from about 14 to about 50 psig at between about 100° C. and about150° C. for a period of from about 0.5 to about 15 hours.

Generally, any of the polymers disclosed in co-pending patentapplication Ser. No. 021,053, filed 03/02/87, now U.S. Pat. No.4,801,400 entitled Epoxy Pyrrolidone Based Non-Ionic Surfactants, may beemployed as a suitable polymeric moiety for complexing with iodine orbromine.

The preparation of the present complex is achieved by an economical andcommercially feasible process. More particularly, iodine, bromine or amixture of halogen and the corresponding hydrogen halide or inorganichalide salt such as the sodium or potassium salt of iodine or bromine iscontacted with the pyrrolidonyl surfactant polymer. The mole ratio ofhalogen to hydrogen halide or inorganic halide salt employed in thepresent process is between about 2:1 and about 10:1, preferably betweenabout 3:1 and about 8:1 and the concentration of halogen based onpolymer is between about 10% and about 50% by weight, preferably betweenabout 20% and about 30% by weight. The vapor pressure of the halogenduring complexing is reduced essentially to zero providing a stablecomplexed product.

The complexing reaction is effected at a temperature between about 20°and 85° C., preferably between 40° and about 60° C. with constantagitation under atmospheric pressure. The addition of halogen plushalide solution to polymer is accomplished in a period of from 5 minutesto 2 hours, preferably from about 20 to 45 minutes.

The complexed products of this invention can be formulated as aconcentrate with disinfecting washing formulations and concentrations ofthe present complexes between about 0.1 and about 15 weight % of activeingredients are effective in providing an increased non-foamingcleansing action coupled with germicidal and insecticidal disinfectingproperties. The optimum weight concentration of the present complexes inthe concentrate formulation falls within the range of from about 0.8 toabout 5 weight %.

A typical disinfectant and cleaning concentrate is represented by theformulation:

    ______________________________________                                        Components               wt. %                                                ______________________________________                                        halophor complex, e.g.   8.75                                                  ##STR4##                                                                     phosphoric acid (75%)    8.0                                                  iodophor base (nonionic) 5.0                                                  water                    78.25                                                ______________________________________                                    

The above formulation has 1.75% available iodine Aliquats of 25 to 100ppm iodine can then be made up as the disinfectant cleaning solution.The resulting solutions are lower foaming than conventional products, asdemonstrated in the following examples, and are milder to the skin andstable at elevated temperatures over extended periods.

Reference is now made to the following examples which illustratepreferred embodiments but which are not to be construed as limiting tothe scope of the invention as more broadly set forth above and in theappended claims.

EXAMPLE 1

Preparation of ##STR5##

To 41.2 g. (0.2 mole) of nonylphenol in a round bottom flask was added0.4 g. of potassium hydroxide. The mixture was heated to 120° C. undervacuum to remove water, after which 112.8 g. (0.8 mole) ofN-epoxypropylpyrrolidone was added at a temperature of from 115° C. to125° C. over a period of 1.5 hours. After addition, the resultingmixture was held at about 115° C. for an additional 3 hours. The mixturewas then cooled and then neutralized with 0.4 g. of glacial acetic acid.The product had a cloud point of 70.5°-71° C. (1% in water).

The iodophor of the above Example was prepared by adding 49.7 g. ofiodine over a period of 30 minutes to a solution of 140 g. ofnonylphenol-4N-epoxypropyl-2-pyrrolidone adduct, in 13.3 g. of watercontaining 17.6 g. of sodium iodide at a temperature of 40°-45° C. Afterthe addition, the reaction mixture was held for 2 hours at 40°-45° C.The resulting iodine complex was found to have 22.5% available iodine.

EXAMPLE 2

Preparation of ##STR6##

To 76.4 g. (0.2 mole) of nonylphenol-4 ethylene oxide adduct (IGEPAL CO430) was added over a period of 2 hours at a temperature of 115°-120°C., 112.8 g. (0.8 mole) of 2,3-epoxypropyl-2-pyrrolidone. After theaddition, the reaction mixture was held at 145° C. for 4 hours afterwhich the product was cooled to room temperature. The product had acloud point above 100° C. The iodophor of the above product was preparedby adding 49.7 g. of iodine over a period of 30 minutes to a solutioncontaining 140 g. of the epoxypropylpyrrolidone polymer obtained abovein 13.3 g. of water containing 17.6 g. of sodium iodide at a temperatureof 40°-45° C. After the addition, the reaction mixture was held for 2hours at 40°-45° C. to form the corresponding complexed compound.

EXAMPLE 3

Preparation of ##STR7##

To 37.2 (0.2 mole) of dodecanol was added 0.4 g. potassium hydroxide andthe mixture was sparged for 30 minutes at 110°-115° C. with nitrogen. Tothis mixture was added over a 2 hour period, 141.0 g. (1.0 mole) of2,3-epoxypyrrolidone and the resulting reaction mixture was held for anadditional 3 hours at 110°-120° C. The product was then cooled and thenneutralized with glacial acetic acid and was found to have a cloud pointof 67°-68° C. (1% in 10% NaCl).

The iodophor of the above compound is prepared according to the methodsset forth in Example 1 employing 49.7 g. of iodine, 140 g. polymer, 13.3g. water and 17.6 g. sodium iodide.

EXAMPLE 4

Preparation of ##STR8##

To a one liter autoclave was charged 85 g. (1.0 mole) of pyrrolidone and0.5 g. of sodium hydroxide flakes. To this mixture was added 580 g. (10moles) of propylene oxide over a period of 5 hours at a temperature of160° C. under 15-30 psig. The resulting mixture was agitated for 30minutes at 160° C., after which it is cooled to 65° C. and a housevacuum was applied to degas the mixture. The product (434 g.) wasneutralized to a pH of 7.4 by addition of phosphoric acid. Productanalysis by NMR indicated that 9.7 of the propylene oxide molecules hadreacted.

EXAMPLE 5

Preparation of ##STR9##

To a one liter autoclave was charged 266.0 g. (0.4 mole) of thepyrrolidone-10 propylene oxide adduct from Example 4 and 176.0 g. (4.0moles) of ethylene oxide was added over a period of 5 hours at 140°-160°C. under a pressure of 15 to 30 psig. The mixture was held at thistemperature for an additional 30 minutes, after which the product 434 g.was cooled, discharged and neutralized with 85% phosphoric acid. By NMRanalysis, it was found that the product contained 8.4 moles of ethyleneoxide. The product was found to have a cloud point of 67° C. (1% inwater).

The iodophor of the above product was prepared by adding to 139.4 g.(0.126 mole) of the above pyrrolidone-PO-EO adduct at a temperature of40°-45° C., 13.3 g. of water containing 17.6 g. of sodium iodide. Tothis solution was added over a period of 30 minutes, 49.7 g. (0.39 mole)of iodine and the resulting mixture was held for an additional 2 hoursat 40°-45° C. The complexed product recovered was found to have 20.6%available iodine and 28.7% total iodine.

EXAMPLE 6

Preparation of ##STR10##

Example 4 was repeated except that 20 moles of propylene oxide issubstituted therein. NMR analysis showed that 20 moles of propyleneoxide had reacted. The material was found to be insoluble in water.

EXAMPLE 7

Preparation of ##STR11##

Using 0.4 mole of the product of Example 6, the procedure set forth inExample 5, reacting 4.0 moles of ethylene oxide is repeated. Theresulting product has a cloud point of 38° C. (1% in water).

The iodophor of the product of this Example is prepared by adding 12 g.of water containing 13.4 g. of sodium iodide at 40° C. to 105.2 g. (0.06mole) of the product of this Example. After the solution is clear, 37.9g. (0.15 mole) of iodine was added over a 0.5 hour period. The resultingreaction mixture was held for 2 hours at 40° to 45° C. Analysis showedthat the resulting iodophor product had 20.7% available iodine and 29.2%total iodine. This complexed compound was stable over 2 weeks at 50° C.and did not deposit iodine when diluted with water.

EXAMPLE 8

Preparation of ##STR12##

To 110.0 g. (1.29 moles) of pyrrolidone containing 0.5 g. of sodiumhydroxide flakes, was gradually added 560 g. (12.9 moles) of ethyleneoxide. After 5 hours, the product was cooled and analysis by NMR showedthat 10.6 moles of ethylene oxide had reacted.

EXAMPLE 9

Preparation of ##STR13##

To 200 g. (0.38 mole) of 2-pyrrolidone-10-EO adduct obtained by Example8 was added 440 g. (7.0 mole) of propylene oxide at a temperature of160° C. under 30 psig pressure. After 5 hours the resulting product wasneutralized with phosphoric acid and was found to have a cloud point of39° C. (1% in water). NMR analysis indicated that 18 moles of propyleneoxide had reacted.

The iodophor of the above product is prepared by adding 20.6 g. ofsodium iodide in 18.6 g. of water to 168.5 g. (0.1 mole) of thepyrrolidone-EO-PO adduct at 40°-45° C. To this mixture, 56.5 g. (0.22mole) of iodine is added and the resulting mixture stirred for 2 hoursat 40°-45° C. Analysis showed that the complexed product contained 19.4%available iodine and 28.0% total iodine. This product was stable for 2weeks at 50° C.

EXAMPLE 10

Preparation of ##STR14##

Example 9 is repeated except that 23.5 moles of propylene oxide issubstituted therein. NMR analysis indicated that 23.5 moles of PO hadreacted. The iodophor of this product is prepared by the procedureoutlined in Example 9.

EXAMPLE 11

Preparation of ##STR15##

To the product of Example 10 is added 10 moles of ethylene oxide at atemperature of 160° C. under 30 psig. After 30 minutes the product iscooled and neutralized and analysis indicated the cloud point to be40°-43° C. (1% in water).

The iodophor of the above product is prepared by adding to 189 g. (0.08mole) of the above adduct obtained in Example 11, at a temperature of40°-45° C., 29.0 g. of sodium iodide in 22.0 g. of water and 83.2 g. ofiodine. The mixture is held for 2 hours at 40°-45° C., after which theproduct is cooled to room temperature. Analysis showed that theresulting iodophor product contained 23.12% available iodine and 32.9%total iodine.

EXAMPLE 12

Preparation of ##STR16##

Into a one liter autoclave was charged 302.5 g. (0.1 mole) of propyleneglycol (molecular wt. 3025) and 0.2 grams of potassium hydroxide. Themixture was heated to 110°-115° C. and held for 1 hour with a nitrogensparge. Over a period of 30 minutes, 84.6 g. (0.6 mole) of2,3-epoxypropyl-2-pyrrolidone was charged to the above solution and,after the addition was completed, the resulting mixture was held for 2hours at 115° C. The product was then cooled and neutralized with 0.2 g.of glacial acetic acid. The product had a cloud point of 17.5°-18° C.(1% in water).

The iodophor of the above adduct was made according to the methoddescribed in Example 1 except that the adduct of Example 12 issubstituted therein.

EXAMPLE 13

Preparation of ##STR17## wherein the sum of x and y is 30.

N-Epoxypropyl pyrrolidone homopolymer having a number average molecularweight of 1900 is prepared by the method of F. P. sidelkovskaya(Vysokomol. Soedin Ser. B, 10(3), 187-189, 1968). To 1900 g or 1 mole ofthe homopolymer is added 0.1 wt. % of potassium hydroxide and 30 molesof propylene oxide at a temperature of 110°-125° C. under 50 to 75 psig.After all propylene oxide is reacted or taken up (about 7 hours) theresulting copolymer is cooled neutralized with phosphoric acid, andrecovered by washing with water and drying.

The iodophor of the copolymer product is prepared by adding about 50 g.of iodine over a period of 30 minutes to a solution of 150 g. of thecopolymer product in 13.3 g. of water containing 17.6 g. of sodiumiodide at a temperature of 40°-45° C. The reaction mixture is thenallowed to stand for 3 hours at 40°-45° C. after which it is cooled andrecovered. The resulting iodine complex has at least 20% availableiodine.

EXAMPLE 14

The extended time release and stability of the following iodophors weremeasured after 2 weeks at 50° C. The results of these tests are reportedbelow.

Compound tested Cloud Point 1% in H₂ O

    __________________________________________________________________________    Compound tested                                                               __________________________________________________________________________       ##STR18##           Cloud Point 1% in H.sub.2 O                            B                                                                                ##STR19##                                                                  C                                                                                ##STR20##                                                                  D                                                                                ##STR21##                                                                                         Initial %      Final* %                                                       Available                                                                           % Total                                                                            Ratio                                                                             Available                                                      Iodine                                                                              Iodine                                                                             I.sup.- -I                                                                        Iodine                                  __________________________________________________________________________    E Iodine Complex of A  20.60 28.7 0.30                                                                              19.55                                   F Iodine Complex of B  20.70 29.2 0.30                                                                              19.90                                   G Iodine Complex of C  19.45 28.0 0.30                                                                              19.45                                   H Iodine Complex of D  23.12 32.96                                                                              0.35                                                                              21.93                                   __________________________________________________________________________     *after 2 weeks at 50° C.                                          

EXAMPLE 15

The low foaming or foam deterrent properties of the following iodophorswere tested using the standard Waring blender test. A 180 ml sample ofeach of the following formulations was mixed at high speed for 3minutes. The initial foam height immediately after mixing was measured,and the foam height was remeasured after 5 minutes. The results of thesetests are as follows:

    ______________________________________                                        Formulation      I       II      III   IV                                     ______________________________________                                        Nonionic Surfactants                                                          Igepal CO-660 (1)                                                                              30.00 g                                                      Compound A of Ex. 14     30.00 g                                              Compound B of Ex. 14             30.00 g                                      Compound D of Ex. 14                   30.00 g                                Iodophor                                                                      I-Complex of Igepal CO-660                                                                     46.00 g                                                      I-Complex E in Ex. 14    46.00 g                                              I-Complex F in Ex. 14            46.00 g                                      I-Complex H in Ex. 14                  46.00 g                                75% Phosphoric Acid                                                                            83.75 g 83.75 g 83.75 g                                                                             83.75 g                                Propylene Glycol 20.00 g 20.00 g 20.00 g                                                                             20.00 g                                Distilled Water  70.25 g 70.25 g 70.25 g                                                                             70.25 g                                ______________________________________                                         (1) C.sub.9 H.sub.19 --C.sub.6 H.sub.4 --O--(CH.sub.2 CH.sub.2 O).sub.10      CH.sub.2 CH.sub.2 OH                                                     

Foam Test

    ______________________________________                                        Formulation  Initial Foam                                                                             Foam after 5 min.                                     ______________________________________                                        I            17.1 mm    17.1 mm                                               II           14.4 mm     0.0 mm                                               III           8.1 mm     3.6 mm                                               IV            9.0 mm     5.4 mm                                               ______________________________________                                    

Comparison of Formulations II, III and IV containing the alkyleneoxypyrrolidonyl iodophors with formulation I containing closely relatedalkyleneoxy iodophors establish the present iodophors as low foamingagents.

All of the above iodophor products in the foregoing Examples possessexcellent surfactant and disinfectant properties. It is to be understoodthat any of the other polymers set forth in the disclosure can besubstituted in the Examples for the preparation of their correspondingiodophors having the desirable properties of this invention. Alsobromine can be substituted in the examples to provide the correspondingbromophors.

What is claimed is:
 1. The process of adding to a detergent solution aneffective cleansing and disinfecting amount of the halogen complexselected from the group consisting of an iodine complex and a brominecomplex of an alkyleneoxy lactam polymer containing between about 2 andabout 40% halogen and said polymer contains(i) at least one pyrrolidonylunit having the formula ##STR22## wherein a has a value of 1-3; p has avalue of 1-2; m has a value of 0-1; R is a radical selected from thegroup of ##STR23## and wherein R⁴ is hydrogen or methyl; (ii) at leasttwo propyleneoxy unitsor (iii) at least two propyleneoxy units and oneor more ethyleneoxy units; and said polymer having terminal groupsselected from the group consisting of hydroxy and the radical ##STR24##wherein R¹ is alkyl having from 6 to 20 carbon atoms; Y is alkyl havingfrom 1 to 4 carbon atoms; v has a value of 0-2 and g has a value of 0-1;and, when m is O, the polymer contains only one of said lactam units,##STR25##
 2. The process of claim 1 wherein the complex is an iodophorand between about 0.1 and about 15 weight % of the iodophor based onactive ingredients is added to the detergent solution.
 3. The process ofclaim 1 wherein said alkyleneoxy lactam polymer has the structure##STR26## wherein at least one of R² and R³ is methyl and the remainingR² and R³ is methyl or hydrogen; h has a total value of 0-100; k has atotal value of 2 to 200 and q has a total value of 0-100 and at leastone of h and q is a positive integer; and R¹, R⁴, Y, g, k, m, p and vare as defined in claim
 1. 4. The process of claim 1 wherein saidalkyleneoxy lactam polymer has the structure selected from the group of##STR27## wherein R⁴ is hydrogen or methyl; s has a value of 2 to 200; thas a total value of 2 to 50; u has a total value of 2 to 50; EO isethyleneoxy and PO is propyleneoxy.
 5. The process of claim 1 whereinsaid alkyleneoxy lactam polymer has the structure ##STR28## wherein nhas a total value of 1-100; m has a value of 0 or 1; t has a total valueof 2-50; u has a total value of 2-50; k has a total value of 2-200; EOis ethyleneoxy and PO is propyleneoxy.
 6. The process of claim 1 whereinsaid alkyleneoxy lactam polymer has the structure ##STR29## wherein khas a total value of 2-200; n has a total value of 1-100; m has a valueof 0 or 1; w has a total value of 1-25; x has a total value of 1-25; EOis ethyleneoxy and PO is propyleneoxy.
 7. The process for extending thegradual release of halogen which comprises adding to a topical medicinalsolution an effective disinfecting amount of the halogen complexselected from the group of a iodine complex and a bromine complex of analkyleneoxy lactam polymer containing between about 2 and about 40%halogen and said polymer contains(i) at least one pyrrolidonyl unithaving the formula ##STR30## wherein a has a value of 1-3; p has a valueof 1-2; m has a value of 0-1; R is a radical selected from the group of##STR31## and wherein R⁴ is hydrogen or methyl; (ii) at least twopropyleneoxy units or (iii) at least two propyleneoxy units and one ormore ethyleneoxy units; and said polymer having terminal groups selectedfrom the group consisting of hydroxy and the radical ##STR32## whereinR¹ is alkyl having from 6 to 20 carbon atoms; Y is alkyl having from 1to 4 carbon atoms; v has a value of 0-2 and g has a value of 0-1; and,when m is O, the polymer contains only one of said lactam units,##STR33##
 8. The process of claim 7 wherein said alkyleneoxy lactampolymer has the structure ##STR34## wherein at least one of R² and R³ ismethyl and the remaining R² and R³ is methyl or hydrogen; h has a totalvalue of 0-100; k has a total value of 2 to 200 and q has a total valueof 0-100 and at least one of h and q is a positive integer; and R¹, R⁴,Y, g, k, m, p and v are as defined in claim
 1. 9. The process of claim 7wherein said alkyleneoxy lactam polymer has the structure selected fromthe group of ##STR35## wherein R⁴ is hydrogen or methyl; s has a valueof 2 to 200; t has a total value of 2 to 50; u has a total value of 2 to50; EO is ethyleneoxy and PO is propyleneoxy.
 10. The process of claim 7wherein said alkyleneoxy lactam polymer has the structure ##STR36##wherein n has a total value of 1-100; m has a value of 0 or 1; t has atotal value of 2-50; u has a total value of 2-50; k has a total value of2-200; EO is ethyleneoxy and PO is propyleneoxy.
 11. The process ofclaim 7 wherein said alkyleneoxy lactam polymer has the structure##STR37## wherein k has a total value of 2-200; n has a total value of1-100; m has a value of 0 or 1; w has a total value of 1-25; x has atotal value of 1-25; EO is ethyleneoxy and PO is propyleneoxy.
 12. Theprocess of claim 7 wherein the complex is an iodophor and between about0.1 and about 15 weight % of the iodophor based on active ingredients isadded to the medicinal solution.